Manufacture of 5-hydroxymethyl 2-furfural



June 12, 195.6 Q. P. PENlsToN MANUFACTURE OF' 5-HYDROXYMETHYL. Z-FURFURAI..

2 Sheets-Sheet l Filed May 22, 1952 0 M M 5 M M w /0 20 30 40 50 o 70 0 ,0a 100 /la /Z INVENTOR/ zz'z' j. .39225195079 BY QM,4//

ATTORNEY June l2, 1956 Q. P. PENISTON MANUFACTURE OF 5-HYDROXYMETHYL 2F`URF`URAL Filed May 22, 1952 2 Sheets-Sheet 2 INVENTOR,

ATTORNEY United States Patent fOce Patented June 12, 1956 MANUFACTURE F SJHYDRXYMETHYL Z-FURFURAL Quintin P. Peniston, Seattle, Wash., assignor to Food Chemical and Research Laboratories, Inc., Seattle, Wash., a corporation of Washington Application May 22, 1952, serial No. 289,397y

11 claims. (ci. 26o-347.3)

The present invention relates to the manufacture of S-hydroxymethyl 2-furfural, hereinafter designated HMP, from carbohydrate substances or mixtures containing keto-hexcse sugars.

It is known to produce HMP by the kdehydration of hexose sugars in an acid media at elevated temperatures, said HMP having been initially prepared in 1895 from levulose by Dull, Chem. Ztg., 19 216, and from sucrose by Kiermayer, Chem. Ztg., 19 1003. Since the work of Dull and Kiermayer over fty years ago, many subsequent investigators have worked along the lines of Dull and Kiermayer, but have not succeeded in producing a practical method for the production of HMP.

It may be pointed out that due to the poor yields obtained by the prior art processes and the unsatisfactory nature of these processes, HMP has never become a starting material for chemical synthesis although it has 'many possibilities.

Using modications of the Kiermayer process, Haworth; Jones and Wiggins, J. Chem. Soc., 1945, 1; -Haworth and Jones, ibid. 1944, 667; and Montgomery and Wiggins, J. Soc. Chem. 1nd. .66, 31 (1947), have studied the yields of HMP obtainable by various vcarbohydrate sources. These investigators have used different acid catalysts, varied conversion temperatures, and an inert atmosphere of hydrogen during the conversion process in an attempt to obtain increased yields or" HMP. They ascertained that higher yields could be produced than had been produced by the processes of previous workers, and HMP could be formed from sucrose without .the use of an added catalyst when higher temperatures were employed. The acidic substancesformedfromthe sucrose under the conditions of conversion were VAsufficient to catalyze the HMP formation. Based on'this work,.:Ha worth and Wiggins obtained U. S. PatentNo. 2,498,918, February 28, 1950, and British Patents No. 591,858 kand No. 600,871. Haworth and his coworkers vmadenodetailed study of the kinetics of HMP formation'landiits destruction when HMP is produced by dehydration of hexose sugars at an elevated temperature in an acid media.

A detailed study has been made of the kinetics of HMP formation and destruction, and it has been discovered how to produce high yields of this material, and this is the primary object of the present invention.

It is desired to pointout that increased yields canbe obtained if the HMP formation reaction velocityconstant k1 increases more rapidly with increasing temperaturethan the HMP destruction reaction velocity constant k2 increases, and that the increase can be effected byconduct ing the reaction to produce HMP at higher temperatures than previously used, and preferably with shorter periods of reaction, and that this increase in yield can be obtained by having present during the conversion ofthe sugar into HMP an aliphatic alcohol, preferably althoughnot necessarily, having 1 to 5 carbon atoms infitstmolecule. Both the Vhigh temperature and the luse offanvaccelerator :of HMP per mole of ketohexoseor equivalent sugar in Vtied by methanol or ethanol.

of HMP formation relative to HMP decomposition may be simultaneously employed to increase the yield.

In one form of the invention where HMP is produced in a linear operation in the presence of alcohol functioning as an accelerator of HMP formation, the alcohol may be one that isvmiscible with the water containing the sugar in solution as, for example, sucrose or levulose, at the temperature of conversion, such alcohol being typi- However, in order to increase the yield of HMP it is desirable to employ a recycling process, and when doing so, it is preferable to use an alcohol which is `miscible with water or the aqueous solution undergoing reaction at a reaction temperature used to convert the sugar to HMP, but not miscible at temperatures below the reaction temperature. Por example, normal butanol is not miscible with water or the aqueous solution undergoing reaction at temperatures below C. and, therefore, when the reaction medium contains butanol, the reaction can be carried out at temperatures above .125 C. as, for example, 130, 140, 150, 160, and 170 Grand upto about 200 C. or about 225n C. On cooling below 125 C. the reaction mixture separates .into two phases, an alcohol rich phase, and an aqueous phase, and it is the latter which vcan be recycled as hereinafter set forth in detail.

The reaction may be carried out with or without an fextraneously added catalyst, but it is preferable to use a catalyst. Any prior art catalyst, including .acid catalysts, and acid-generating catalysts, maybe employed.

'.However, it isfpreferred to carry out the reaction in the Ypresence of an yacid catalyst including inorganic acids and iorganicacids or compounds generating during the reac- 'tion an inorganic or organic catalyst radical, subject to the .limitation that the catalyst should be stable at the .temperature yat which the sugar solution is reacted to pro- .'duce HMP. Por example, oxalic acid cannot be used where the temperature of reaction exceeds C. since it decomposes into forrnic acid and carbon dioxide, -but it can be usedif the temperature of reaction is below 140 C. The preferred catalysts are the strong mineral acids and `particularly sulfuric acid.

.The concentration of the catalyst in the reaction mix- `ture and Iduring the reaction whereby the sugar is converted into HMP has no signiiicant elfect on the yield of HMP. The velocity constants k1 and k2 are both increased by increased vcatalytic concentration but in the same ratio. Catalyst concentration can be considered as a simple, unique balance between the cost of the catalyst and the cost ofheat and equipment. VHigher catalyst concentration gives shorter reaction periods and greater through-put for the same apparatus. Therefore, it is preferred to have a catalyst present and desirably, although not necessarily, in Va vconcentration in the reaction solution between the limits of about 0.2 normal and 0.02

normal.

In one form of the invention it is desirable to stop the reaction medium, the yield of VHMP in the present disclosure wherever itis referred to being expressed as moles the reaction medium. :This yield may be vtermed maxaSV ,that is, the maximum yield based on the sugar present, theexponent sp being the 'rst letters of sugar and present- 'The maximum yield may also be based on the sugar consumed and,.of course, then the maximum yield is in- -creased. However., the amount of HMP produced per '.unit ofmaterial processed will be reduced. For example,

70 medium at.160 C. vis-65% .expressed asrnoles of HMP jper moleofketohexose, vwhich villustratively lmay be deif thepeak concentration of HMP in the aqueous reaction rivecl from sucrose, it is probably not economical to stop the reaction whereby the sugar is converted, as herein set forth, to I-IMF before at least 50% to 75% of this 65% yield is obtained, considering that the concentration of 65% HMF in the reaction medium is based on the sugar present therein. if the reaction is stopped when the yield is lower, the apparent yield may exceed the 65% HMF yield because more sugar will be left unconsumed, and the nal yield, based on the sugar consumed, will be greater than the apparent maximum yield as will be hereinafter more particularly pointed out.

The present invention will be illustrated by the following examples:

EXAMPLE l.-ONE STAGE CONVERSION OF LEVULOSE AT 170 C.

Levulose in the amount of 500 mg. was dissolved in 0.100 normal sulfuric acid, 25 ml. Aliquot portions of this solution (0.2132 ml. each) and 0.2132 ml. of normal butyl alcohol saturated with water were sealed in small glass tubes and heated in an oil bath at 170 C. for the following time periods: 2, 4, 6, 8, l0, l2 and 16 minutes. After conversion reaction the tubes were cooled rapidly in water, opened and the contents quantitatively transferred to volumetric flasks for dilution to an appropriate concentration for ultraviolet absorption analysis. Optical density of the solutions at 2840 A. (angstrorns) was measured using 1.00 cm. quartz cells in a Bechmann Model DU ultraviolet spectrophotometer. The HMF content of each solution was calculated from the molar extinction coefficient of 16,700 reported by Singh, Dean and Cantor in J. A. C. S. 70, 517, 1948. It may be stated that ultraviolet `analysis for determination of HMF has been recommended by Schou and Abildgaard, Z. Untersuch. Lebensm. 68, 502, 1934. This method of analysis for HMF is accurate for kinetic studies When humidication is not exessive. With strongly overconverted reaction products a correction factor must be applied for ultraviolet absorption by humic substances and levulinic acid. Ultra-violet measurements must be made soon after dilution of the samples since autooxidation of HMF to hydroxymethyl furoic acid proceeds rapidly in very dilute aqueous solutions. In the present experiments the ultraviolet method of analysis has been checked by oxidation of crude HMP extracts to hydroxymethyl furoie acid by the method of Reichstein, Helvetica Chimica Acta, 9, 1066, 1926, and there has been obtained yields of over ninety per cent based on the ultra-violet HMF analysis.

Analytical data for Example 1 HM F Optical Dilution for Yield, Conversion Tune (min.) Analysis Percent of Theory A maximum yield of 68.0% in eight minutes is indicated. From these values and Equations 2 and 3, hereinafter referred to, k1=0.2710, k2=0.0506.

Referring to the above table, the expression dilution for analysis indicates that the entire content of each tube Vamounting to 0.4264 ml. was diluted in water to the volume shown, namely, 100, 200, or 250 ml. This was done to bring the HMF concentration into suitable range for accurate measurement with the spectrophotometer. An optical density of 1.0 means that 1A0 of the ultraviolet light to which the solution was exposed was transmitted, the other W10 being yabsorbed by the HMF. Without dilution less than lA000 of the light would be transmitted, and the instrument would not measure this small amount accurately.

EXAMPLE 2.-TWO STAGE CONVERSION OF SUCROSE Sucrose in the amount of 10.0 grams was dissolved in 0.100 normal sulfuric acid, 50 ml. To this solution was added normal butyl alcohol saturated with water, 50 ml. The mixture was placed in a small stainless steel autoclave and heated in an oil bath at 150 C. for 20 minutes. The autoclave was cooled in water, opened and the phases separated. The alcohol was reddishbrown in color and the aqueous phase pale yellow. There was no solid material. The aqueous phase was extracted with 50 ml. of wet butanol and returned to the autoclave with another 50 ml. of wet butanol for a second conversion using the same time and temperature. After the second conversion the phases were again separated and the aqueous phase was again extracted with 50 ml. of wet butanol. Analytical results are shown in the following table.

Analytical results for Example 2 7 EMF Yield, Phase l Oll'lme Found, :Percent c grains I Theory Butanol after lstl conversion 5l) 1. 230 33, 4 Extract from Aqueous Phase, 1st Conversion 50 0. 474 12. 9 Butanol after 2nd Conversion 50 0. 593 16. l Extract from Aqueous Phase, 2nd Conversion 50 0. 228 6. 2 Final Aqueous Residue. 50 0. 143 3. 9

Total HMF formed percent.. 72. 5 Total BMF recovered in butanol extracts do 68. 6 Estimated sugar consumed do 86 Recovered Yield based on sugar consumed do 80.0

EXAMPLE 3.-'1`WO STAGE CONVERSION OF BLACK-STRAP MOLASSES Crude black-strap molasses (71.5% dry substance, 47.9% total sugar) in the amount of grams was diluted with 100 ml. of water and de-ashed by passage over a column of cation exchange resin. Eiuent and washings to 250 ml. were collected. Fifty milliliters of this solution equivalent to 20 grams of original molasses was mixed with 50 ml. of wet butanol and converted in a stainless steel autoclave at C. for 20 minutes. No catalyst other than the acids liberated by ash removal was used. Phase separation on cooling was not as rapid as with sucrose but was still satisfactory. The aqueous phase was extracted with 50 ml. of wet butanol and then again converted for 20 minutes at 150 C. with 50 ml. of added wet butanol. The phases were again separated and the aqueous phase again extracted with a 50 ml. portion of wet butanol. Analytical results were as follows:

Analytical results for Example 3 HMF Yiclri, Phase Vollme Found, Percent o grams Theory i Butauol after 1st Conversion 50 t). 759 l 21.5 Extract from Aqueous Phase, 1st Gonversion' 48 0.231 i 6.5 Butanol after 2nd Conversion 53 0. 396 i 114 2 Extract from Aqueous Phase, 2nd Gonversion 5l 0. 143 4. u Final Aqueous Phase 49 0.094 2. 7

Total l'IMF recovered in butanol cxtracts per cent" 43.2

EXAMPLE 4 SUCROSE CONVERSIONS WITH VARYING AMOUNTS OF BUTANOL Mixtures of sucrose, sulfuric acid, dry normal butyl alcohol and water were prepared as follows:

Series A-sucrose, 10 parts; water, 100 parts; butanol,

none; sulfuric acid, 0.100 normal in mixture Series B-sucrose, parts; water, 84 parts; butanol, 16

parts; sulfuric acid, 0.100 normal in mixture SeriesC-sucrose, 10 parts; water, 68 parts; butanol, 32

parts; sulfuric acid, 0.100 normal in mixture Series D-sucrose, 10 parts; water, 52 parts; butanol, 48

parts; sulfuric acid, 0.100 normal in mixture Aliquot portions of these mixtures were converted in small glass tubes at 150 C. for various time periods, namely, 5, 10, 15, 20, 25, and 30 minutes. After conversion the tubes were cooled, opened and the contents 'diluted for ultraviolet analysis. Results were as follows:

HMF founaL-percent of theory Conversion Time (min.) Series A Series B Series C Series D Reactions of HMF formation and `destruction Coloring matter Insoluble humin It has been discovered that the rate controlling step in reactions of HMP formation is of pseudo-first order type, i. e. the rate is proportional to the concentration of the primary reactant and to the catalyst concentration. At low sugar concentrations the humification is of negligible importance so that only the main chain of reactions need be considered. Under these conditions the well known kinetics of consecutive first crder reactions will apply'. It may thus be shown that the maximum yield of the intermediate (HMF) obtainable in a one Stage process is dependent on the values of the reaction velocity constants, k1 and k2 and is independent of the Vconcentration of the starting material, k1 being the HMF formation reaction velocity constant, and k2 being the HMF destruction reaction velocity constant. lThe relationships involved are expressed in the following equations and are illustrated graphically in the accompanying drawing designated Figure 1.

Fraction of sugar as k1 HMF at time 0 (them-mie-W-erkl (l) Time to maximum:

In Figure 1 experimentally determined values yof the rate constants for a onepercent levulose solution in'onetenthnormal :sulfuric -acid Vat 130 and 15 0 degreesA centigrade have lbeen used toplot Equations 1 and 4, above at -the two temperatures. VCurves for 130 C. indicate a maximum yield of HMF based on the sugar originally present of 41.5% at about 100 minutes reaction time. However, at this time 32% vof the sugar still remains so that the yield based onsugar consumed is 61%. At 150 C. the maximum occurs at only 19 minutes and amounts to 51.6% based on original sugar or 68.3% based on sugar consumed. Moreover, if this reaction were to be stopped at 10 minutes instead of 19, the yield of HMF based on sugar consumed'would be 83%. It is apparent from a consideration of Fig. 1 that when the reaction rates are increased by higher temperatures the time to the maximum Abecomes more sharply defined. It is also apparent from Equation 2 and Fig. 1 that if the reaction velocity constant k1 can be increased relative to k2 the maxima for the curves will attain higher values, and this can be accomplished by the use of higher reaction temperatures and by use of an aliphatic monohydric alcohol.

It is desired to point out that Equations 2 and 3 may be solved to obtain the values of the velocity reaction con* stants k1 and k2 which have to be satisfied in order to attain the desired yield. These are set forth in the following table:

Reaction Yield Desired, Percent Dslfd 1:, In la/ki minutes 1 3. 67 o. 1046 35. 1 90 10 0. 367 0. 0104s 35. 1 100 0. 0367 0. 001046 35. 1 1 2.72 0. 223 12. 2 8O 10 0. 272 O. 0223 12. 2 100 0. 0272 o. 00223 12. 2

1 2. 20 o. 345 0. 3s 10 0. 220 o. 0345 e. 3s .100 o. 0220 0. 00345 e. 3s 1 1. 74 511 3. 33 00 10 0.174 0. 0511 3. 33 100 o. 0174 0. 00511 a. 33

Referring to the above' table, it is'to be noted that the ratio of k1/ k2idetermines the yield and that the time tothe maximum varies inversely with both constants. The ratio of ki/kz is slightly less than doubled for a 10% yincrease in yield 'between 60 and 80%. However, a much Vgreater increasefin the ratio is necessary in order to provide a to 90% yield of HMF. Yields as high as 80% maybe obtainableby increasing the temperature to about 200 C., with 225 C. as the top limit. Therefore, a broad range for the ratio of Ici/k2 is from about 1.5 to about 25.0, this covering yields from 50 to 85%. k1 may vary from 0.1 to about 6.0 and k2 from 0.05 to 0.25, or morezbroadly from 0.01 to about 6.0 and k2 from .0007 to 0.25.

It is desired to point out .that previous workers in the field-relating to the production of HMF have not been aware that if the ratio k1/k2 was maintained as herein set forthv that the yield of HMF could be increased, and more specifically that the prior investigators did not know that high yields could be obtained if the HMF formation reaction velocity constant k1 was increased relative to the HMF destruction constant k2. It has been discovered that the HMF Vformation reactionv constant increases more 'rapidly withincreasing' temperature than does the velocity Yof 'the HMF vdestruction reaction constant. This effect is shown graphicallyin Fig. 1.

It is desired to'poi'nt out that the beneficial effect of the alcohols used in carrying out the present invention may varywith the concentration of the alcohol in aqueous solution. It appears that the molar ratio of the alcohol is an important factor and that this molar ratio may vary vbetween the'limits of 0.1/and 0.4, and for preferred re- 'sultsthe'molarratio of alcohol'to water should be about 0.3. In Example4results with 48% normal butyl alcohol were only slightly better than with 32%. The rate kof grp.

heat exchanger 2 and is separated into alcohol-rich and aqueous phases in a decanter 3. The alcohol-rich phase from the decanter 3, containing most of the HMF, coloring matter, and organic acids, is combined with the extract from the extractor 6 and is purified in a continuous, counter-current scrubber 4 using dilute sodium hydroxide solution and a bottom redux of butanol. The purified butanol solution of HMF is concentrated to a sirup in a vacuum still 5. The aqueous phase from the decanter 3 is further extracted in a continuous, counter-current eX- tractor 6 the raiiinate from which is concentrated in an evaporator 7 and glucose is removed in a crystallizer 3. The levulose-enriched raffinate is recharged to the converter .l with new raw material. Butanol and water from the still are reused in the process.

What is claimed is:

l. In the method of producing 5-hydroxymcthyl Z-l'urfural by heat-reacting under pressure in the presence of an acidic catalyst and between the temperature limits of about 130 C. and about 225 C. an aqueous solution of a keto-hexose sugar, said catalyst being stable at the temperature at which the sugar solution is reacted, the step of acceleratingr the rate of formation of the S-hydroxymethyl 2-furfural relative to the rate of its decomposition by having present in said aqueous solution an unsubstituted, saturated aliphatic monohydric alcohol having from l to 5 carbon atoms in its molecule, the molar ratio of the alcohol to the water in said solution being between the limits of 0.1 and 0.4.

2. In the method of producing 5-hydroxymethyl Z-furfural by heat-reacting under pressure in the presence of a catalyst and between the temperature limits of about 130 C. and about 225 C. an aqueous solution of a ketohexose sugar, said catalyst being selected from the group of catalysts consisting of hydrochloric acid, hydrobromic acid, phosphoric acid, sulfuric acid, zinc chloride and aluminum chloride, the step of accelerating the rate of formation of the S-hydroxymethyl 2-furfural relative to the rate of its decomposition by having present in said aqueous solution. an unsubstituted, saturated aliphatic monohydric alcohol having from 1 to 5 carbon atoms in its molecule, the molar ratio of the alcohol to the water in said solution being between the limits of 0.1 and 0.4.

3. ln the method of producing 5hydroxymethyl 2-furfural by heat-reacting under pressure in the presence of a catalyst and between the temperature limits of about 130 C. and about 225 C. an aqueous solution of a ketoheXose sugar, said catalyst being selected from the group of catalysts consisting of hydrochloric acid, hydrobrornic acid, phosphoric acid, sulfuric acid, zinc chloride and aluminum chloride, the step of accelerating the rate of formation of the 5hydroxymethyl 2-furfural relative to the rate of its decomposition by having present in said aqueous solution an unsubstituted, saturated aliphatic monohydric alcohol miscible with water at the reaction temperature, said alcohol having from l to 5 carbon atoms in its molecule, but immiscible with water at a temperature between the limits of about 25 C. and about 40 C., the molar ratio of the alcohol to the water in said solution being between the limits of 0.1 and 0.4.

4. In the method of producing 5hydroxymethyl 2-furfural by heat-reacting under pressure in the presence of a catalyst and between the temperature limits of about 130 C. and about 225 C. an aqueous solution of a ketohexose sugar, said catalyst being selected from the group of catalysts consisting of hydrochloric acid, hydrobromic acid, phosphoric acid, sulfuric acid, zinc chloride and aluminum chloride, the step of accelerating the rate of formation of 5-hydroxymethyl 2furfural relative to the rate of its decomposition by having butanol present in said aqueous solution, the molar ratio of the butanol to the water in said solution being between the limits of 0.1 and 0.4.

5. The method defined in claim 1 in which the catalyst is a strong mineral catalyst.

6. The method deined in claim 2 in which there is present in solution a strong mineral acid catalyst having a concentration between the limits of about 0.02 normal and 0.2 normal.

7. The method defined in claim 3 in which there is present in solution a strong mineral acid catalyst having a concentration between the limits of about 0.02 normal and 0.2 normal.

8. The method of producing S-hydroxymethyl 2-furfural comprising forming a mixture of an aqueous alcoholic solution of a keto-hcxose sugar having a sugar concentration between the limits of about 2.5% and about 20%, and a catalyst selected from the group of catalysts consisting of hydrochloric acid, hydrobromic acid, phosphoric acid, sulfuric acid, zinc chloride and aluminum chloride, said catalyst accelerating the formation of the neto sugar into S-hydroxymethyl 2-furfural, said aqueous alcohol solution comprising water and an unsubstituted, saturated aliphatic monohydric alcohol having from 1 to 5 carbon atoms in its molecule, said alcohol functioning to increase the rate of formation of the 5hydroxymethyl 2furfural at the reaction temperature, and reacting the resulting mixture at a temperature between the limits of about C. and about 225 C., the molar ratio of the alcohol to the water in said solution being between the limits of 0.1 and 0.4.

9. The method of producing S-hydroXymethyl 2-furfural comprising forming a mixture of an aqueous alcoholic solution of a keto-hexose sugar having a sugar concentration between the limits of about 2.5% and about 20%, and a catalyst selected from the group of catalysts consisting of hydrochloric acid, hydrobromic acid, phosphoric acid, sulfuric acid, zinc chloride and aluminum chloride7 said catalyst accelerating the formation of the keto sugar into S-hydroxymethyl 2 urfural, said catalyst being present in solution in a concentration between the limits of about 0.02 and about 0.2 normal, said aqueous alcohol solution comprising water and an unsubstituted, saturated aliphatic monohydric alcohol having from 1 to 5 carbon atoms in its molecule, said alcohol functioning to increase the rate of formation of the S-hydroxymethyl 2-furfural at the reaction temperature, the water being present in a predominating proportion, said alcohol being miscible with the water at the reaction temperature, and reacting said mixture at a temperature between the limits of about 130 C. and about 225 C., the molar ratio of the alcohol to the water in said solution being between the limits of 0.1 and 0.4.

10. The method defined in claim 1 in which the catalyst is sulphuric acid.

11. In the method of producing 5-hydroxymethyl 2- furfural comprising heat-reacting under pressure and between the temperature limits of about 130 C. and about 225 C. an aqueous solution of a keto-hexose sugar, the step of accelerating the rate of formation of the 5- hydroXymethyl 2-furfural relative to the rate of its decomposition by having present in said aqueous solution an unsubstituted, saturated aliphatic monohydric alcohol having from 1 to 5 carbon atoms in its molecule, the molar ratio of the alcohol to the water in said solution being between the limits of 0.1 and 0.4.

References Cited in the tile of this patent UNITED STATES PATENTS 2,498,918 Haworth et al Feb. 28, 1950 FOREIGN PATENTS 591,858 Great Britain Sept. l, 1947 600,871 Great Britain Apr. 21, 1948 OTHER REFERENCES Handbook of Chem. and Physics, 24th ed., p. 818, No. 4057 (1940).

Haworth et al.: Chem. Soc. Jour. (1944), part I, pp. 667-670. 

1. IN THE METHOD OF PRODUCING 5-HYDROXYMEHTYL 2-FURFURAL BY HEAT-REACTING UNDER PRESSURE IN THE PRESENCE OF AN ACIDIC CATALYST AND BETWEEN THE TEMPERATURE LIMITS OF ABOUT 130* C. AND ABOUT 225* C. AN AQUEOUS SOLUTION OF A KETONE-HEXOSE SUGAR, SAID CATALYST BEING STABLE AT THE TEMPERATURE AT WHICH THE SUGAR SOLUTION IS REACTED, THE STEP OF ACCLERATING THE RATE OF FORMATION OF THE 5-HYDROXYMETHYL 2-FURFURAL RELATIVE TO THE RATE OF ITS DECOMPOSITION BY HAVING PRESENT IN SAID AQUEOUS SOLUTION AN UNSUBSTITUTED, SATURATED ALIPHATIC MONOHYDRIC ALCOHOL HAVING FROM 1 TO 5 CARBON ATOMS IN ITS MOLECULE, THE MOLAR RATIO OF THE ALCOHOL TO THE WATER IN SAID SOLUTION BEING BETWEEN THE LIMITS OF 0.1 AND 0.4 